Structural and spectral studies of N-(4-chloro)benzoyl-N′ -2-tolylthiourea

Article abstract of DOI:10.1016/S0022-2860(03)00371-5

The crystal and molecular structure of N-(4-chloro)benzoyl-N′ -2-tolylthiourea (C₁₅H₁₃N₂OSCl, M_r = 304.79) is determined by X-ray diffraction. The crystal structure is monoclinic, space group P2₁In wi

Full text of DOI:10.1016/S0022-2860(03)00371-5

Journal of Molecular Structure 657 (2003) 215–223
www.elsevier.com/locate/molstruc
0
Structural and spectral studies of N-(4-chloro)benzoyl-N -2-
tolylthiourea
a,
Zhou Weiqun , Leng Kuisheng , Zhang Yong , Lude Lu
a
a
b
*
a
Department of Chemistry and Chemical Engineering, Suzhou University, 1 Shizi Street, Suzhou, JiangSu 215006, China
b
Institute of Chemical Engineering, Nanjing University of Science and Technology Nanjing, Nanjing 210094, China
Received 11 December 2002; revised 30 May 2003; accepted 5 June 2003
Abstract
0
The crystal and molecular structure of N-(4-chloro)benzoyl-N -2-tolylthiourea (C15
H
13
N
2
OSCl, M ¼ 304:79) is determined
r
by X-ray diffraction. The crystal structure is monoclinic, space group P2 =n with a ¼ 3:9898ð3Þ; b ¼ 22:922ð2Þ; c ¼ 16:005ð2Þ
1
ꢀ
ꢀ 3
3
A; b ¼ 104:367ð4Þ8; V ¼ 104:367ð4Þ A ; Z ¼ 4; D ¼ 1:428 g=cm : The results of extended MO calculations using density
c
functional theory (DFT) with a hybrid B3LYP density functional approximation and FTIR and NMR studies on the title
compound are reported. With the basis sets of the 6-311G* quality, the DFT calculated bond parameters, harmonic vibrations
and chemical shifts are in a very good agreement with experimental data. The intramolecular and intermolecular hydrogen
bonds are discussed. Non-linear optical properties of the molecule are predicted.
q 2003 Elsevier B.V. All rights reserved.
Keywords: N-Benzoyl thiourea; Crystal structure; Hydrogen bonds; Density functional theory; NMR spectra
1
. Introduction
properties. A variety of crystals of this class have
been communicated [6–10]. In the present study, we
have synthesized a new substituted thiourea, N-(4-
Non-linear optical materials have found appli-
0
chloro)benzoyl-N -2-tolylthiourea.
cations in the areas of laser technology, optical
communication and data storage technology in the
last few years. Thiourea molecule has large dipole
moment [1] and has the ability to form extensive
network of hydrogen bonds. Single crystals of
thiourea, and an inorganic complex have evoked
much interest due to their non-linear optical properties
X-ray diffraction, vibration spectroscopy (IR) and
NMR techniques are widely used to study structural
and dynamic aspects of various molecular systems.
With the recent advances in computer hardware
and software, it is possible to correctly describe
chemical properties of relatively small molecules
[
11–16] with highest chemical accuracy using
[2–5]. Substitutions that reduce the symmetry of the
thiourea molecule enhance the non-linear optical
classical methods based on self-consistent field
molecular orbital Hartree–Fock theory (SCF-MO
HF). The achieved accuracy is generally improved
in more advanced calculations which include
electron correlation (e.g. Moller–Plesset second
*
Corresponding author. Tel.: þ86-5126-5325-112; fax: þ86-
5126-5112-853.
E-mail address: wqzhou@suda.edu.cn (Z. Weiqun).
0022-2860/03/$ - see front matter q 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-2860(03)00371-5

216
Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
order approximation, MP2). The importance of size,
presence of polarization and diffuse functions in
the basis set used for a proper theoretical description
of the molecules which include multiple bonds,
heteroatoms and lone electron pairs is also well
recognized [11,12]. On the other hand, the density
functional theory (DFT) is less computationally
demanding in predicting physical properties of
molecular systems [12,17–21] at the MP2 level
of accuracy or better. To shed more light on
the accurate prediction of geometry and IR spectro-
scopic and NMR characteristics of the title compound
in the gas phase, a detailed DFT calculation has been
performed.
a Kofler melting point apparatus: 163–164 8C
(uncorrected).
2.2. Crystal structure determination
A light yellow crystal with dimensions of
3
0.31 £ 0.62 £ 0.11 mm is mounted on a glass fiber.
All measurements are made on a Rigaku Mercury
CCD area detector with graphite monochromatic
ꢀ
Mo Ka radiation ðl ¼ 71073 AÞ: The data are
corrected for Lorentz and polarization effects. The
structure is solved by direct methods [22] and
expanded using Fourier techniques [23]. The non-
hydrogen atoms are refined anisotropically. Hydrogen
atoms are refined using the riding model. The
crystal structure is of monoclinic, space group P2 =n
1
ꢀ
2
. Experimental
with a ¼ 3:9898ð3Þ; b ¼ 22:922ð2Þ; c ¼ 16:005ð2Þ A;
3
1:428 g=cm :
3
ꢀ
b ¼ 104:367ð4Þ8 V ¼ 104:367ð4Þ A ; Z ¼ 4; D ¼
c
2
.1. Synthesis and physical methods
In the present study, the sample is synthesized by
condensation of 4-chlorobenzoyl chloride with
2.3. Method of calculation
NH SCN in solution of dry acetone. The mixture is
4
Initio molecular geometry is optimized using semi-
empirical PM3 methods (HYPERCHEM 5.0, Hypercube,
Ont., Canada). In the next step, the DFT calculation are
performed with the GAUSSIAN 98 software package [9]
reacted with 2-methyl aniline. The final product is
easily separated and this thiourea is estimated from
Fig. 1 reaction. Melting points are determined on
Fig. 1. The reaction process.

Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
217
using 6-311G* basis set. The DFT calculation with a
hybrid functional B3LYP (Becke’s Three parameter
Hybrid Functional Using the LYP Correlation Func-
tional) [24–26] are selected. The optimized structure
showed positive harmonic vibrations that (Nimag ¼ 0)
indicated only a true energy minimum [11,12,16]. The
harmonic vibration frequencies are calculated for the
optimized structure of the molecule to obtain the force
constants using the same model chemistry. The GIAO
method [12,16,18] is using for prediction of nuclear
shielding using the same method. Because shielding
constants reported in experimental studies are usually
shifts relative to a standard compound, often tetra-
methylsilane (TMS), we also compute the absolute
shielding value for TMS, using exactly the same model
chemistry due to compare predicted values to exper-
imental results. The single point energy and dipole
moments are calculated using 6-311þþG** basis set.
listed in Table 1. In the molecule of the crystal, the C–
˚
N bond such as C(13)–N(1) (1.342 A), N(2)–C(14)
˚
˚
(1.390 A), N(1)–C(14) (1.361 A) and N(2)–C(9)
˚
(1.420 A) is shorter than the normal C–N bond length
˚
(1.4685 A), which revealed that C–N bond is of the
character of double bond. It is deduced that this
thiourea makes up a multi-electron conjugated p
bond. There are no significant differences in the bond
distances and bond angles comparing with other
phenyl thiourea [6–10]. N(2)–C(14) I is longer than
˚
N(1)–C(14) by 0.02 A, similar to the other benzoyl
thiourea [8,9], which is probable due to the electron
withdrawing effect of the carbonyl group. Two aryl
rings are basically parallel. Comparing with -(2-
0
pyridiny)-N -benzoylthiourea, The angle between the
two aryl is 22.248, larger than that of thiourea [10]. The
benzoyl ring is at a little larger angles to the thiourea
moiety. The angle between the phenyl ring and the
thiourea moiety (O(1)C(13)N(1)C(14)N(2)) is 33.518,
similar to it. The biggest angle attaching the tolyl ring
to the thiourea moiety (O(1)C(13)N(1)C(14)N(2)) is
3
. Results and discussion
51.028. Substitution on the phenyl ring decrease the
3
.1. Structure studies
planarity; torsional steric and electrostatic repulsion
and intramolecular hydrogen bond can also increase
this effect (Fig. 2).
The crystal data and the refinement detail are
deposited with other materials at Cambridge-struc-
ture, and selected bond parameters together with the
optimized structure parameters using DFT method are
A intramolecular hydrogen bonding is between
N(2)H(13) and benzoyl oxygen and non-bonding
˚
N(2)· · ·O(1)distance, 2.569A, isshorter than theN· · ·O
Table 1
The selected bond parameters DFT calculated of and experimental
˚
Bond lengths (A)
Experiment
DFT
Bond angles (8)
Experiment
DFT
Cl(1)–C(10)
1.749(7)
1.679(9)
1.248(9)
1.342(11)
1.361(11)
1.420(11)
1.390(10)
1.491(10)
1.541(11)
1.7528
1.6720
1.2251
1.3813
1.4082
1.4360
1.3417
1.5065
1.4964
C(13)–N(1)–C(14))
C(1)–N(2)–C(14)
N(2)–C(1)–C(2)
N(2)–C(1)–C(6)
C(1)–C(6)–C(15)
C(5)–C(6)–C(15)
C(8)–C(7)–C(13)
C(12)–C(7)–C(13)
Cl(1)–C(10)–C(9)
Cl(1)–C(10)–C(11)
O(1)–C(13)–N(1)
O(1)–C(13)–C(7)
N(1)–C(13)–C(7)
S(1)–C(14)–N(1)
S(1)–C(14)–N(2)
N(1)–C(14)–N(2)
127.12(6)
121.5(7)
126.5(8)
114.2(7)
124.0(7)
119.7(7)
117.0(7)
121.6(8)
115.7(7)
118.3(6)
125.0(7)
117.7(7)
117.3(6)
120.2(6)
125.4(7)
114.4(7)
129.4917
124.7415
118.3477
120.2781
121.4024
121.4647
117.1614
123.7873
119.3886
119.4678
122.9886
121.3211
115.6874
118.0444
126.6898
115.2652
S(1)–C(14)
O(1)–C(13)
N(1)–C(13)
N(1)–C(14)
N(2)–C(1)
N(2)–C(14)
C(6)–C(15)
C(7)–C(13)
Dihedral angle
C(14)–N(1)–C(13)–O(1)
C(14)–N(1)–C(13)–C(7)
C(13)–N(1)–C(14)–S(1)
C(13)–N(1)–C(14)–N(2)
SP energy (a.u.)
6.1
176.4
176.7
2.2
3.8402
176.7702
179.6555
0.6161
6-311þþG**
2
1622.83691
2.0946
Dipole moment (Debye)

218
Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
13 2
Fig. 2. Molecular structure of C15H N OSCl.
0
distance found for N-benzoyl-N -p-methoxyphenyl
C(7)–C(12), C(10)–C(11) bonds are longer, while
N(2)–C(14), C(4)–C(5), C(7)–C(13), O(1)–C(13)
bonds are shorter than experimental values, which are
due to that the theoretical calculations refers to a free
state (isolated), while experimental data are obtained
by single crystal X-ray crystallography.
˚
thiourea, 2.618 A [8]. Another intramolecular hydro-
gen bond is between C(8)–H(5)· · ·O(1), non-bonding
˚
distance, 2.848 A, formed bifurcated hydrogen bond
together with the former. The intermolecular hydro-
gen bonding for the title compound, however, appears
to be weaker compared to the bis(2-pyridyl)thioureas
based on longer N(2)–H(12)· · ·S(2) non-bonding
distance. The intermolecular interactions in crystals,
3.2. IR analysis
˚
mostly occurred between Cl(1) and H(11A), is 2.95 A,
˚
the distance of S(1)–H(5A) is 2.65 A, and the
˚
distance of S(1)–H(12A) is 2.64 A, which affect the
FTIR spectra are obtained in KBr discs using a
Nicolet 170SX FT-IR spectrometer. FTIR spectrum is
shown in Fig. 4. The strong absorbing nCyO band in
the IR spectra of the compound appears at about
form of crystal packing. The intramolecular and
intermolecular hydrogen bond parameters are shown
in Table 2. Because of these intense intramolecular
interactions, the barriers to single bond rotating
are formed consisting of the special local structure.
The title compound crystallizes, is kept in an acentric,
symmetric and conjugated situation; this situation
should be propitious to the enhancing of non-linear
optical properties.
2
1
1670.5 cm , apparently decreasing in frequencies
comparing with the ordinary carbonyl absorption
Table 2
The intramolecular and intermolecular hydrogen bonds
A–H· · ·B
Experiments Calculations
N(2)H(13)· · ·O(1)
N(2)· · ·O(1)
N(2)H(13)
2.569(9)
0.950(2)
1.823(9)
2.57822
1.0221
DFT predicted stable conformation is shown in
Fig. 3. The conformer structure parameters, dipole
moment and single point energies are gathered in
Table 1 with comparing experimental data. The
predicted thermodynamics energies are given in
Table 3. The agreement between the theoretically
calculated and the experimentally obtained structure
parameters for the thiourea is very good. The
discrepancies between the X-ray and the fully
optimized structure are manifested in the bond length
and bond angles in the title compound. Such
the calculated N(1)–C(3), N(1)–C(14), N(1)–C(13),
O(1)· · ·H(13)
1.87184
N(2)H(13)O(1) 133.2(8)
C(8)–H(5)· · ·O(1) C(8)· · ·O(1)
C(8)H(5)
2.848(10) 2.77541
0.950(2)
0.97820
H(5)· · ·O(1)
2.619(10) 2.480884
94.1(7)
C(8)H(5)O(1)
N(1)–H(12)· · ·S(2) N(1)· · ·S(2)
N(1)H(12)
3.595(6)
0.950(8)
2.653(6)
H(2)· · ·S(2)
N(1)H(12)S(2) 171.4(6)
˚
distance, A; angle, 8.

Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
219
Fig. 3. The optimized conformer of the thiourea using B3LYP/6-311G*.
2
1710 cm ). This is interpreted by the result of its
1
(
difference of frequencies between the calculation and
the experiment can be considered as the difference of
the state. Usually, the molecular vibration frequencies
in the gas state are larger than in the solid.
conjugated resonance with the phenyl ring and the
possible formation of intramolecular hydrogen bond-
ing with N–H. In addition, the abnormal intensity
2
1
ratio between nCyO and dN–H (1535 cm ) bands
revealed that intramolecular hydrogen bonding might
From frequency calculation we have obtained
static non-linear optical hyperpolarizabilities b and
g of designed compound with the B3LYP/6-311G*
method of GAUSSIAN program, in which we used the
perturbation theory and b and g equation (Eqs. (1)–
(3)) obtained according to the program
2
1
exist in this compound. The peak 3263.8 cm
attributed nN(1)–H(12), the relative weak peaks 3128.8,
is
2
1
3
055.5 and 3024.6 cm
are attributed nN(2)–H(13),
which also reveal the existence of intramolecular
hydrogen bond.
It is well known, that the calculated RHF and DFT
bI ¼ bI11 þ bI22 þ bI33
ð1Þ
‘
raw’ or ‘non-scale’ harmonic frequencies could
g ¼ 1=5½g
þ g
þ g
XXXX
YYYY
ZZZZ
significantly overestimate experimental values due
to lack of electron correlation, insufficient basis sets
and anharmonicity. Much effort has been devoted to
accurately reproduce experimental frequencies in
theoretical calculations. The Hartree–Fock calculated
results are usually more overestimated than the
corresponding DFT ones [24]. Therefore, we selected
DFT (B3LYP) method to predict harmonic vibrations.
The vibration frequencies are given in Table 4
together with partly intensive FTIR absorption data.
The theoretical spectra along with the experimental
one are shown in Fig. 4. By comparing calculational
and the experimental data, we obtained functional
formula shown in Table 5. The scale factor 0.97746 is
obtained from this equation. The linear properties of
the equation are very satisfactory. So, the predicted
vibration frequencies are suitable for comparison with
experiments. The major discrepancy existed in
relative absorption intensity is in reason [12]. A little
þ 2:0ðgXXYY þ gXXZZ þ gYYZZ
Þ
ð2Þ
ð3Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
x
2
y
2
z
bvec
¼ b þ b þ b
Table 3
The dipole moment, thermodynamics energy (a.u.)
The dipole moment (Debye)
2.4570
298.150
Tempertature (K)
Pressure (atm)
1.0000
0.250230
Zero-point correction (Hartree/Partical)
Thermal correction to energy
0.267020
Thermal correction to enthalpy
Thermal correction to Gibbs free energy
Sum of electionic and zero-point energies
Sum of electionic and thermal energies
Sum of electionic and thermal enthapies
Sum of electionic and thermal free energies
0.267964
0.204122
21622.537714
21622.520924
1622.519980
21622.583822

220
Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
Fig. 4. Experimental FTIR spectrum, together with the theoretical DFT(B3LYP)/6-311G*.
static non-linear hyperpolarizability values are shown
that bvec ¼ 187:86 £ 10
of the thiourea. Enhancing conjugation and
dissymmetry can increase hyperpolarizabilities.
According Tadeusz Pluta et al. calculation [25], the
232
esu; The compound is
certainly not of interest as a non-linear optical
material for the second-harmonic generation as well
third-harmonic generation of single thiourea is
235
2
32
as the thiourea 158.5 £ 10
esu. The g ¼ 681:98 £
about 10
well as thiourea.
esu. It will raise the same interest as
2
39
239
1
0
esu was larger than 7.127 £ 10
esu

Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
221
Table 4
DFT(B3LYP)/6-311G* harmonic vibrational frequencies (non-scaling)
21
21
21
21
21
21
DFT n (cm
)
I (km mol
)
Experiment n (cm
)
Attributed
DFT n (cm
)
I (km mol
)
Experiment n (cm
)
Attributed
3630.6
3439.6
3215.8
3208.3
3202.0
3195.0
3183.3
3178.3
3173.1
3164.4
3112.2
3087.3
3036.2
1727.1
1651.6
1638.9
1628.5
1609.7
1585.9
1563.9
1534.6
1526.5
1516.2
1501.8
1481.5
1436.7
1430.2
1380.8
1337.5
1327.7
1326.7
1312.3
1279.4
1253.8
1217.4
1214.0
1188.5
1175.8
1141.9
1140.7
1108.4
1093.2
1070.3
1069.9
1031.6
29.6
319.99
2.52
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
n
d
n
d
d
n
d
d
d
d
d
n
d
d
d
d
d
d
d
n
d
d
d
n
n
n
N(1)H(12)
N(2)H(13)
Ph)H
Ph)H
Ph)H
Ph)H
Ph)H
Ph)H
Ph)H
Ph)H
CH3
CH3
CH3
C¼O
CC
1014.4
987.1
979.5
965.14
956.5
941.5
879.7
867.87
855.60
833.47
808.56
791.2
770.2
748.0
736.9
724.5
718.2
683.7
665.6
657.8
643.5
613.9
577.4
551.2
526.4
505.3
481.6
459.6
448.1
419.0
385.1
369.2
309.3
279.6
267.0
220.4
178.2
154.3
140.9
109.9
1.17
1.42
0.052
17.31
5.35
0.12
4.57
13.7
20.9
3.03
20.48
8.35
52.45
31.09
25.87
9.14
28.2
5.75
56.36
17.00
5.90
37.87
5.78
31.3
3.15
1.85
22.81
0.57
2.19
0.17
17.14
0.84
0.37
0.78
2.18
4.96
3.74
2.81
3.38
5.71
1.05
0.14
0.31
0.39
0.04
0.04
d
n
n
CCC
CC
3263.8
968.3
941.3
CC
2.49
g
g
g
g
g
g
g
PhH
PhH
PhH
PhH
PhH
PhH
PhH
0.82
20.34
35.15
7.53
3128.8
3055.4
10.51
5.46
3024.1
844.9
794.7
26.34
11.38
20.63
216.4
2.29
n
n
CCl
CCl
2955.2
1670.5
763.9
736.9
721.4
g
g
g
PhH
PhH
PhH
78.46
10.71
0.17
1593.3
1535.5
CC
d
n
CCC
CC
PhH
CC
690.6
,
l
d
CCC
CC
g
g
g
g
g
512.75
598.87
22.87
93.99
11.79
24.4
CC
PhH
PhH
PhH
PhH
N–H
CC
1485.3
1458.3
N–H
CH3
CC
605.7
t
t
t
t
t
t
t
t
CCCC
CCCC
CCCN
CCCN
CNCN
CCCC
CNCN
CNCN
547.8
517.0
1.56
PhH,
PhH,
PhH
d
d
CH3
18.60
4.42
1400.4
1381.1
1334.8
CH3
478.1
443.3
492.90
6.60
PhH,dN–H
PhH
5.25
1300.1
1265.4
CyS
1.37
PhH,
PhH,
PhH
d
d
CH3
d
d
d
CyS
CCC
CCC
6.72
CH3
108.97
43.04
4.51
PhH, dN–H
t
t
t
CCCC
CCCC
CCCC
1208.4
1196.0
1176.7
1153.3
PhH,
PhH
PhH
d
CH3
34.37
2.34
d
CCC
296.4
3.67
C(S)–N
N–H
t
t
t
t
t
t
t
t
t
CCCC
CCCC
CCCN
CCCN
CCCN
CCCC
CCCC
CCCC
CCCC
60.9
PhH
99.95
29.5
1091.8
1010.8
PhH, nCyS 94.9
CN,dPhH
CN, dPhH
66.4
53.2
37.2
22.1
6.17
4.85
CN
PhH
,
51.14
1
7.9
1
400 instrument. The data of H NMR spectral
3
.3. NMR studied
1
experimental are similar with its derivation [7]. H
0
NMR spectroscopy was recorded in CDCl3 at
room temperature in 400.00 MHz on an INOVA
NMR studies in CDCl3 show the NH hydrogen
resonance considerably downfield from other

222
Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
Table 5
in downfield about d7–8 ppm. The CH3 peak is
shown at 2.3612 ppm.
Analysis linear equation of the vibration frequencies
B3LYP/6-311G*
GIAO NMR nuclear shielding predicted by
DFT(B3LYP)/6-311G* are recalculated to chemical
shifts and compared with experiment (Table 6). The
isotropic shieldings are commonly compared with
experiment. Higher quality of the present DFT
calculations (6-311G*) can predict the correctly
results. The experimental chemical shifts of protons
attached to nitrogen are shifted towards lower
magnetic field by about 2 ppm, as compared with
calculated ones. On contrary, the proton attached
phenyl ring and methyl proton are fairly reproduced
by theory value, each discrepancy is only about
Function
Y ¼ 226:07416 þ 0:97746X
Scale factor
0.97746
0.97746
191.64
34
R
SD
N
P
,0.0001
resonances in the spectrum. The proton of N–H
chemical shift is found about at d12.1743 ppm for
hydrogen bonds, another proton of N–H is about at
d9.1812 ppm, H in benzene resonance is come out
0
.5 ppm downfield in comparison with our predicted
DFT method) values (Table 6). Differences of 10–
0 ppm between the DFT calculation and the
(
2
Table 6
experiment carbon atom nuclear shielding are
observed. In order to find the regulation between the
The NMR shield data of the molecule
1
3
B3LYP/6-311G*
Experiment
CDCl
GIAO DFT (B3LYP)/6-311G* NMR data and
C
(
3
)
chemical shift data of experiments, a linear corre-
lation between our predicted and observed carbon
chemical shifts of the title compound was shown in
Fig. 5. The linear equation is Y ¼ 1:00742 þ
0:9843X; R ¼ 0:9827; SD ¼ 6.8726. This phenom-
enon is caused by H-bonding in condensed phased
and is partly taken into account in Ref. [26] by using
a supermolecule approach which mimics solute–
solvent interactions.
Isotropic
TMS
d
(ppm)
d
(ppm)
(ppm)
(ppm) isotropic
C(1)
39.9401
51.2919
53.0261
50.0261
49.8110
39.3320
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
192.6284
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
31.7906
152.6845
141.3165
139.6023
142.6023
142.8174
153.2964
197.7244
176.4519
144.9463
145.3865
143.2163
163.3572
141.933
138.5537
28.6674
6.7172
167.01
134.25
129.84
147.63
137.41
160.14
203.81
164.16
142.12
150.13
138.15
158.47
148.52
130.94
31.29
C(2)
C(3)
C(4)
C(5)
C(6)
C(14)
C(13)
C(7)
25.0960
16.1765
47.6821
47.2419
49.4121
29.5712
50.6954
54.0747
163.9610
25.0734
24.9506
24.8771
24.9562
24.1356
24.8487
24.9606
24.9565
29.5507
29.9133
30.3357
21.8347
24.5512
C(8)
C(9)
C(10)
C(11)
C(12)
C(22)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
7.2457
6.84
7.5112
7.5402
7.3174
7.8769
7.5481
7.2876
7.3054
2.3612
2.3612
2.3612
12.1743
9.1812
6.9135
6.8388
7.655
6.9432
6.7232
6.8341
2.2399
1.8771
1.4549
Fig. 5. Correlation of theoretical DFT predicted carbon chemical
shifts of the title compound with experiment using 6-311G*
basis set.
9.9559
7.2394

Z. Weiqun et al. / Journal of Molecular Structure 657 (2003) 215–223
223
4
. Conclusions
[11] W.J. Hehre, L. Radom, P.R. Schleyer, J.A. Pople, Ab Initio
Molecular Orbital Theory, Wiley, New York, 1986.
[
12] J.B. Foresman, A. Frisch, Exploring Chemistry with Elec-
tronic Structure Methods, second ed., Gaussian Inc, Pittsburg,
PA, 1996.
According to the X-ray data, in the structure of
2
molecular, both N is of the character of sp . This is the
result of the effect of their neighboring double bonds.
It is deduced that this thiourea moiety makes up a
multi-electron conjugated p bond. An significant
intramolecular hydrogen bond is in the N(2)–
[
13] K. Ruud, T. Helgaker, R. Kobayashi, P. Jorgensen, K.L. Bak,
H.J.A. Jensen, J. Chem. Phys. 100 (1994) 8178.
[14] D.B. Chesnut, in: G.A. Webb (Ed.), Annual Reports on NMR
Spectroscopy, vol. 29, Academic Press, New York, 1994, p.
7
1.
˚
H(13)· · ·O(1), bond distance 2.569 A, bond angle
[
[
15] A.C. de Dios, Prog. Magn. Reson. Spectrosc. 29 (1996) 229.
16] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A.
Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery
Jr., R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam,
A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi,
V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C.
Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala,
Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck,
K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz,
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1
33.28, forming a six-tempered ring with C(13), N(1)
and C(14). There are another intramolecular attraction
of the title compound is between O(1)· · ·H(5)C(5),
formed a bifurcated hydrogen bond together with the
former. FTIR, NMR spectra are also shown the
intramolecular hydrogen bonds. DFT methods used in
calculated molecular structure is believed to be
effective. The performance of the DFT calculated
bond parameters and harmonic vibrations are in a very
good agreement with available experimental data.
Increasing conjugation and dissymmetry of thiourea
will be benefit for non-linear hyperpolarizabilities.
[
[
17] M. Kofranek, T. Kovar, H. Lischka, A. Karpfen, J. Mol. Struct.
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